Selective removing method of carbon monoxide

ABSTRACT

According to the present invention, provided is a method of selectively removing carbon monoxide, comprising the step of preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and the plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed, and the step of introducing a gaseous mixture containing H 2 , CO and an oxidizing agent of O 2  into the catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a high application temperature so as to selectively oxidize and remove CO from the gaseous mixture.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-160615, filed Jun. 8, 1999, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a selective removing method of carbon monoxide.

A polymer electrolyte fuel cell permits suppressing generation of a pollutant causing an air pollution, is high in its heat efficiency and, thus, is expected to be used widely as a low temperature operation type fuel cell in a motor car power source, a dispersed power source or the like. A platinum catalyst is used mainly in the electrode of the polymer electrolyte fuel cell. Since the platinum catalyst tends to be poisoned by carbon monoxide (CO), it is necessary remove CO from the fuel gas as much as possible. The fuel gas is manufactured by, for example, reforming the fuel such as methanol by means of steam reforming reaction or a partial oxidation reaction so as to produce a hydrogen gas. Then, CO formed as a by-product in the hydrogen manufacturing reaction is removed by a CO shift reaction of CO+H₂O→CO₂ +H₂.

The removal of CO by the CO shift reaction is limited under the restriction in terms of the chemical equilibrium. For example, where a hydrogen gas is manufactured from methanol, followed by applying the CO shift reaction to the hydrogen-containing reaction mixture, the resultant gaseous composition contains about 40 to 60% of H₂, about 10% of CO₂, about 20% of H₂O, and about 0.5% of CO. It should be noted that, in order to prevent the polymer electrolyte fuel cell from being poisoned by CO, it is necessary to lower the CO concentration to 100 ppm or lower. Such being the situation, it is necessary to take measures for further lowering the CO concentration in combination with the CO shift reaction. As a particular measure, studied is a method in which an oxidizing agent of O₂ is added to the gaseous mixture after the CO shift reaction, followed by bringing the resultant gaseous mixture into contact with a catalyst capable of selectively oxidizing carbon monoxide so as to selectively oxidize CO within the gaseous mixture for removing CO.

However, the temperature at which the catalyst capable of selectively oxidizing carbon monoxide is allowed to perform its function sufficiently is limited. In addition, the oxidizing reaction of carbon monoxide is an exothermic reaction. Therefore, if the temperature in the reaction atmosphere is elevated with progress of the selective oxidizing reaction, the selective oxidizing capability of the catalyst is lowered, resulting in failure to remove sufficiently carbon monoxide.

On the other hand, Japanese Patent Disclosure (Kokai) No. 6-296870 as claimed discloses a catalyst for cleaning the waste gas. It is taught that the catalyst consists of at least one metal selected from the platinum group elements, which is supported on a crystalline silicate having an X-ray diffraction pattern shown in Table A given in this prior art and represented in terms of the molar ratio of the oxide in a dehydrated state by a chemical formula (1±0.8)R₂O.[aM₂O₃.bM′O.cAl₂O₃]ySiO₂, where R denotes an alkali metal ion and/or hydrogen ion, M denotes an ion of at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, M′ denotes an ion of alkaline earth metals of Mg, Ca, Sr, Ba, 0<a, 0≦b<20, a+c=1, and 11<y<3000.

This prior art also teaches in columns [0008] to [0009] that the particular waste gas cleaning catalyst permits cleaning the waste gas containing NO_(x), CO and HC in accordance with reaction formulas (1) to (4) given below:

C₃H₆+3/2O₂→3CH₂O  (1)

CH₂O+O₂→CO₂+H₂O  (2)

CH₂O+2NO→N₂+CO₂+H₂O  (3)

CO+1/2O₂→CO₂  (4)

Reaction (1) given above represents activation of HC, reaction (2) represents combustion of HC, reaction (3) represents a denitrification, and reaction (4) represents combustion of CO.

BRIEF SUMMARY OF THE INVENTION

An object of the present invention is to provide a method of selectively removing carbon monoxide that permits improving a carbon monoxide removal rate in selectively removing CO from a gaseous mixture containing H₂ and CO.

According to a first aspect of the present invention, there is provided a method of selectively removing carbon monoxide, comprising the steps of:

preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and the plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and

introducing a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ into the catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a high application temperature so as to selectively oxidize and remove CO from the gaseous mixture.

According to a second aspect of the present invention, there is provided a method of selectively removing carbon monoxide, comprising the steps of:

preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and the plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and

introducing a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ into the catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a high application temperature so as to selectively oxidize and remove CO from the gaseous mixture;

wherein the catalyst in each of the plurality of catalyst layers capable of selectively oxidizing carbon monoxide and differing from each other in the temperature of application includes at least one kind of a carrier and an active metal supported on the carrier, the carrier being selected from the group consisting of Y-type zeolite, mordenite, A-type zeolite, γ-Al₂O₃, anatase and a crystalline silicate having the highest to the fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, and having the composition represented by formula (1) under a dehydrated state:

(1±0.8)R₂O.[aM₂O₃.bNO.cAl₂O₃].ySiO₂  (1)

where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000.

According to a third aspect of the present invention, there is provided a method of selectively removing carbon monoxide, comprising the steps of:

preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and the plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and

introducing a gaseous mixture containing H₂, CO and an oxidizing agent Of O₂ into the catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a high application temperature so as to selectively oxidize and remove CO from the gaseous mixture;

wherein at least one kind of the catalyst includes a carrier and an active metal supported on the carrier, the carrier being a crystalline silicate having the highest to the fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, and having the composition represented by formula (1) under a dehydrated state:

(1±0.8)R₂O.[aM₂O₃.bNO.cAl₂O₃].ySiO₂  (1)

where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000.

Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention.

The accompanying FIGURE schematically shows a catalyst bed used in Examples 1 to 25.

DETAILED DESCRIPTION OF THE INVENTION

A method of the present invention for selectively removing carbon monoxide will now be described in detail.

In the method of the present invention, prepared first is a catalyst bed consisting of a plurality of catalyst layers capable of selectively oxidizing carbon monoxide and differing from each other in the temperature of application such that the catalyst layer having a low application temperature is arranged on the upstream side of the catalyst bed. Then, a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ is introduced into a first catalyst layer having a low application temperature so as to permit the catalyst to bring about a selective oxidizing reaction of carbon monoxide. Further, the gaseous mixture coming from the first catalyst layer is introduced into a second catalyst layer, et seq. having an application temperature higher than that of the first catalyst layer so as to permit the catalyst in the second catalyst layer, et seq. to bring about a selective oxidizing reaction of carbon monoxide. The oxidizing agent contained in the gaseous mixture is consumed by the selective oxidizing reaction. Therefore, it is desirable to supply an additional oxidizing agent to the gaseous mixture every time the gaseous mixture is introduced into a new catalyst layer. While passing through the catalyst bed consisting of a plurality of catalyst layers arranged in series, CO contained in the gaseous mixture is selectively oxidized so as to be removed.

The oxygen gas (O₂) contained in the gaseous mixture is for oxidizing CO and, thus, need not be present together with H₂ and CO from the first. The method of the present invention comprises the step of adding an oxidizing agent of O₂ to a raw material gaseous mixture containing H₂ and CO, followed by introducing the resultant gaseous mixture into the catalyst bed. An oxygen gas or the air can be added to the raw material gaseous mixture.

In the catalyst bed, it is desirable for the second catalyst layer, et seq. to have application temperatures adapted for the temperature of the gaseous mixture introduced therein.

The catalyst capable of selectively oxidizing carbon monoxide comprises a carrier and at least one kind of an active metal supported on the carrier. The catalyst capable of selectively oxidizing carbon monoxide can be used as it is in the form of a powder or can be held on a porous support.

The carrier used in the present invention is selected from the group consisting of Y-type zeolite, mordenite, A-type zeolite, γ-Al₂O₃, anatase-type TiO₂ and a crystalline silicate having the highest to the fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, and having the composition represented by formula (1) under a dehydrated state:

(1±0. 8)R₂O.[aM₂O₃.bNO.cAl₂O₃].ySiO₂  (1)

where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000.

The same carrier or a plurality of different carriers can be used for preparing a plurality of catalysts capable of selectively oxidizing carbon monoxide and differing from each other in the application temperature.

If the crystalline silicate fails to exhibit peaks at the five lattice spacing in the powder X-ray diffraction using a CuKα ray, or if the peaks, even if exhibited, fail to be any of the highest to the fifth highest peaks, it is impossible to selectively oxidize CO. It is desirable for the crystalline silicate to exhibit the highest to the fifth highest peaks in the powder X-ray diffraction using a CuKα ray at the five lattice spacing and to exhibit the sixth highest peak et seq. in the lattice spacing of 3.0±0.1 Å, 3.3±0.1 Å, 4.25±0.1 Å, 5.6±0.2 Å, 6.0±0.2 Å, and 6.4±0.2 Å. It is more desirable for the crystalline silicate to exhibit the highest to the eleventh highest peaks in the powder X-ray diffraction using a CuKα ray at the eleven lattice spacing and exhibit the twelfth highest peak et seq. at the lattice spacing of 3.05±0.1 Å, 4.6±0.1 Å, 5.7±0.2 Å, and 6.7±0.2 Å.

It is desirable to use the crystalline silicate among the carriers exemplified above.

The active metal supported on the carrier should be at least one kind of metal selected from the group consisting of Pt, Pd, Ru, Rh and Ir.

In selecting a plurality of catalysts differing from each other in the application temperature from among the catalysts capable of selectively oxidizing carbon monoxide, it is desirable to select a catalyst having Pt supported as an active metal on the carrier and another catalyst having at least one active metal selected from Pd, Ru, Rh and Ir supported on the carrier.

It is desirable to control the temperature of the gaseous mixture to fall within a range of between 50° C. and 280° C. when the gaseous mixture is introduced into the catalyst bed. If the temperature of the gaseous mixture is lower than 50° C., the selectivity of the catalyst capable of selectively oxidizing carbon monoxide tends to be markedly lowered. On the other hand, if the temperature of the gaseous mixture exceeds 280° C., the reaction rate of a side reaction of 2H₂+O₂→2H₂O is increased. As a result, the oxidizing reaction of CO tends to be suppressed, resulting in failure to obtain a high CO removal rate.

It is desirable for the CO concentration in the gaseous mixture containing H₂, O₂ and CO to be not higher than 4% when the gaseous mixture is introduced into the catalyst bed. If the CO concentration exceeds 4%, the reaction heat tends to be markedly elevated by the combustion heat generated by the combustion reaction of carbon monoxide, with the result that the selectivity of the catalyst capable of selectively oxidizing carbon monoxide tends to be lowered.

According to the method of the present invention described above for selectively removing carbon monoxide, a plurality of catalysts capable of selectively oxidizing carbon monoxide and differing from each other in the application temperature are prepared and arranged in series in the order of the application temperature starting with the catalyst having the lowest application temperature so as to form a catalyst bed. In the present invention, a gaseous mixture containing H₂, CO and an oxidizing agent of O₂is introduced into the catalyst bed through the first catalyst layer having the lowest application temperature to permit the catalyst in the first catalyst layer to bring about a selective oxidizing reaction of CO. It should be noted that heat is generated by the selective oxidizing reaction so as to elevate the temperature of the gaseous mixture. However, an additional oxidizing agent is supplied to the gaseous mixture when the gaseous mixture is introduced into the second catalyst layer having an application temperature higher than that of the first catalyst layer so as to bring about again a selective oxidizing reaction of CO. It follows that the carbon monoxide removal rate can be increased.

Where at least three catalyst layers differing from each other in the application temperature are arranged in series to form a catalyst bed, the carbon monoxide oxidizing reaction is carried out in the presence of the catalysts in the first and second catalyst layers as in the case where the catalyst bed consists of the first and second catalyst layers. Then, an additional oxidizing agent is supplied to the gaseous mixture having the temperature elevated as a result of the reactions in the first and second catalyst layers, followed by introducing the gaseous mixture into the third catalyst layer having the application temperature higher than that of the second catalyst layer so as to bring about again the selective oxidizing reaction of CO. The carbon monoxide removal rate can be further increased by repeating the operation of supplying the gaseous mixture into the succeeding catalyst layer having an application temperature higher than that of the preceding catalyst layer after supply of an additional oxidizing agent into the gaseous mixture.

In the method of the present invention, it is desirable to use in combination a first catalyst capable of selectively oxidizing carbon monoxide, said first catalyst including a carrier and an active metal of Pt supported on the carrier, and a second catalyst capable of selectively oxidizing carbon monoxide, said second catalyst including a carrier and at least one kind of an active metal selected from Pd, Ru, Rh and Ir, said active metal being supported on the carrier. In this case, the application temperature of the first catalyst capable of selectively oxidizing carbon monoxide is lower than that of the second catalyst capable of selectively oxidizing carbon monoxide. As a result, a CO removal rate can be further increased because the application temperatures of the catalysts are increased stepwise in accordance with the temperature elevation caused by the selective oxidizing reaction.

In the present invention, it is particularly desirable to use a crystalline silicate having a composition represented by aforementioned formula (1) under a dehydrated state and having the highest to the fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, as a carrier of at least one of the first and second catalysts capable of selectively oxidizing carbon monoxide. In this case, it is possible to improve the carbon monoxide removal rate. The reasons for the improved carbon monoxide removal rate are considered to be as follows.

Specifically, the particular crystalline silicate specified in the present invention is hydrophobic so as to be unlikely to be affected by water that is present together, has a strong charge density distribution, and has fine pores sized about 6 Å and, thus, adapted for the CO adsorption. As a result, the crystalline silicate specified in the present invention is capable of selectively adsorbing a polar substance of CO. It should also be noted that any of Pt, Pd, Ru, Rh and Ir supported on the crystalline silicate exhibits a high activity so as to adsorb O₂ contained in the gaseous mixture. As a result, CO adsorbed on the crystalline silicate can be preferentially oxidized by O₂ adsorbed on the active metal as denoted by reaction formula (A) given below, though side reactions (a) to (c) also take place to some extent so as to improve the selective oxidizing capability of the catalyst and, thus, to improve the carbon monoxide removal rate:

2CO+O₂→2CO₂  (A)

2H₂+O₂→2H₂O  (side reaction (a))

CO₂+H₂→CO+H₂O  (side reaction (b))

CO+3H₂→CH₄+H₂O  (side reaction (c))

The method of the present invention can be used for refining a hydrogen-based fuel gas used in a polymer electrolyte fuel cell.

To be more specific, in order to obtain the fuel gas, a hydrogen gas is manufactured by applying a reforming reaction such as a steam reforming reaction or a partial oxidation reaction to methanol or hydrocarbons such as gasoline or methane. It should be noted that CO formed by a side reaction is contained in the reformed gas. Carbon monoxide contained in the reformed gas is removed in two stages. In the first stage, the CO concentration is lowered to a desired value by, for example, a CO shift reaction. Then, the residual CO is removed by the method of the present invention. To be more specific, the air or an oxygen gas is supplied to the gaseous material having the CO concentration lowered to a desired level. Also, a plurality of catalysts capable of selectively oxidizing carbon monoxide and differing from each other in the application temperature are prepared and arranged in series in the order of the application temperature such that the catalyst having a low application temperature is arranged in the front stage so as to form a catalyst bed. Then, the gaseous material having the CO concentration lowered to a desired level is introduced into the catalyst bed through the catalyst layer having a low application temperature. Further, an additional oxidizing agent is supplied to the gaseous material before introduction of the gaseous material into the second catalyst layer, et seq. having higher application temperatures so as to permit the catalysts in the second catalyst layer, et seq. to perform their catalyst selectivity to remove CO. As a result, the selective oxidizing reaction of CO takes place over the entire region of the catalyst bed so as to improve the CO removal rate and to obtain a hydrogen-based fuel gas for a polymer electrolyte fuel cell having CO removed therefrom to a desired level, e.g., not higher than 100 ppm.

Some examples of the present invention will now be described in detail.

In the first step, honeycomb catalysts 1 to 24 used in the Examples of the present invention were prepared as follows.

Honeycomb Catalyst 1:

Water-glass No. 1 (SiO₂:30%) was dissolved in an amount of 5,616 g in 5,429 g of water to prepare solution A. On the other hand, dissolved in 4,175 g of water were 718.9 g of aluminum sulfate, 110 g of ferric chloride, 47.2 g of calcium acetate, 262 g of sodium chloride, and 2,020 g of a concentrated hydrochloric acid to prepare solution B. These solutions A and B were supplied at predetermined rates into a container to form precipitation, and the mixture was sufficiently stirred to obtain a slurry having a pH value of 8. The slurry was charged in an amount of 20 liters (L) into an autoclave, followed by introducing 500 g of tetrapropyl ammonium bromide into the autoclave to carry out a hydrothermal synthesis at 160° C. for 72 hours. After the synthesis, the reaction mixture was washed with water and, then, dried, followed by sintering the mixture at 500° C. for 3 hours so as to obtain crystalline silicate 1 having a composition shown in Table 1 under a dehydrated state.

A powder X-ray diffraction measurement using CuKα ray was applied to the resultant crystalline silicate 1 to obtain lattice spacing (d value) and relative intensities of the highest peak to the 15th highest peak, which are shown in Table 2.

As apparent from Table 2, the crystalline silicate 1 exhibited in the powder X-ray diffraction using a CuKα ray the highest to the fifth highest peaks at the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, the sixth highest to the eleventh highest peaks at the lattice spacing of 3.0±0.1 Å, 3.3±0.1 Å, 4.25±0.1 Å, 5.6±0.2 Å, 6.0±0.2 Å, and 6.4±0.2 Å, respectively, and the twelfth highest to the fifteenth highest peaks at the lattice spacing of 3.05±0.1 Å, 4.6±0.1 Å, 5.7±0.2 Å, and 6.7±0.2 Å, respectively.

The crystalline silicate 1 was dipped in a 4N NH₄Cl aqueous solution maintained at 40° C. and the solution was kept stirred for 3 hours so as to carry out the NH₄ ion exchange. After the ion exchange, the crystalline silicate 1 was washed and, then, dried at 100° C. for 24 hours, followed by sintering the crystalline silicate at 400° C. for 3 hours so as to obtain the H-type crystalline silicate 1.

Then, a carrier consisting of 100 parts of the H-type crystalline silicate 1 was impregnated with an aqueous solution of chloroplatinic acid (H₂PtCl₆) to permit 0.6 part by weight of platinum to be supported by the crystalline silicate 1, followed by evaporating the solvent for the drying purpose and subsequently performing sintering at 500° C. for 5 hours so as to obtain a powdery catalyst.

A binder consisting of 3 parts of alumina sol (Al₂O₃:10%) and 55 parts of silica sol (SiO₂: 20 parts) was added to the resultant powdery catalyst together with 200 parts of water, and the aqueous system was sufficiently stirred to prepare a slurry for wash coating. Then, a monolithic substrate made of cordierite ceramics and having 400 cell lattice meshes was dipped in the slurry. After the substrate was taken out of the slurry, the slurry attached to the substrate was blown off, followed by drying the substrate at 200° C. The coating amount was 140 g per liter of the monolithic substrate, and the coated substrate constituted the honeycomb catalyst 1.

Honeycomb Catalysts 2 to 12:

Crystalline silicates 2 to 12 having the compositions as shown in Table 1 under a dehydrated state were prepared as in preparation of honeycomb catalyst 1 described above, except that cobalt chloride, ruthenium chloride, rhodium chloride, lanthanum chloride, cerium chloride, titanium chloride, vanadium chloride, chromium chloride, antimony chloride, gallium chloride and niobium chloride were added in place of ferric chloride used in preparation of honeycomb catalyst 1 in a molar amount equal to Fe₂O₃ in terms of oxides.

A powder X-ray diffraction measurement using a CuKα ray was applied to each of these crystalline silicates 2 to 12, finding that the lattice spacing and the relative intensities of the highest to the fifteenth highest peaks were as shown in Table 2.

Then, honeycomb catalysts 2 to 12 were prepared as in preparation of honeycomb catalyst 1 described above.

Honeycomb Catalysts 13 to 15:

Crystalline silicates 13 to 15 having the compositions as shown in Table 1 under a dehydrated state were prepared as in preparation of honeycomb catalyst 1 described above, except that magnesium acetate, strontium acetate and barium acetate were added in place of calcium acetate used in preparation of honeycomb catalyst 1 in a molar amount equal to CaO in terms of oxides.

A powder X-ray diffraction measurement using a CuKα ray was applied to each of these crystalline silicates 13 to 15, finding that the lattice spacing and the relative intensities of the highest to the fifteenth highest peaks were as shown in Table 2.

Then, honeycomb catalysts 13 to 15 were prepared as in preparation of honeycomb catalyst 1 described above.

Honeycomb Catalyst 16:

A carrier consisting of 100 parts of an H-type crystalline silicate 1 equal to that described previously in conjunction with honeycomb catalyst 1 described previously was impregnated with an aqueous solution of palladium chloride to permit 0.6 part by weight of Pd to be supported by the carrier, followed by evaporating the solution and drying the carrier impregnated with palladium and subsequently sintering the carrier at 500° C. for 5 hours so as to obtain powdery catalyst. Further, a honeycomb catalyst 16 was prepared from the powdery catalyst by the method equal to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 17:

A carrier consisting of 100 parts of an H-type crystalline silicate 1 equal to that described previously in conjunction with honeycomb catalyst 1 described previously was impregnated with an aqueous solution of rhodium chloride to permit 0.6 part by weight of Rh to be supported by the carrier, followed by evaporating the solution and drying the carrier impregnated with rhodium and subsequently sintering the carrier at 500° C. for 5 hours so as to obtain powdery catalyst. Further, a honeycomb catalyst 17 was prepared from the powdery catalyst by the method equal to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 18:

A carrier consisting of 100 parts of an H-type crystalline silicate 1 equal to that described previously in conjunction with honeycomb catalyst 1 described previously was impregnated with an aqueous solution of ruthenium chloride to permit 0.6 part by weight of Ru to be supported by the carrier, followed by evaporating the solution and drying the carrier impregnated with ruthenium and subsequently sintering the carrier at 500° C. for 5 hours so as to obtain powdery catalyst. Further, a honeycomb catalyst 18 was prepared from the powdery catalyst by the method equal to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 19:

A carrier consisting of 100 parts of an H-type crystalline silicate 1 equal to that described previously in conjunction with honeycomb catalyst 1 described previously was impregnated with an aqueous solution of iridium chloride to permit 0.6 part by weight of Ir to be supported by the carrier, followed by evaporating the solution and drying the carrier impregnated with rhodium and subsequently sintering the carrier at 500° C. for 5 hours so as to obtain powdery catalyst. Further, a honeycomb catalyst 19 was prepared from the powdery catalyst by the method equal to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 20:

A powdery catalyst was prepared by impregnating an H-type Y-zeolite powder with an aqueous solution of chloroplatinic acid to permit 0.6 part by weight of Pt to be supported by the zeolite powder. Then, a honeycomb catalyst 20 was prepared by the method similar to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 21:

A powdery catalyst was prepared by impregnating an H-type mordenite powder with an aqueous solution of chloroplatinic acid to permit 0.6 part by weight of Pt to be supported by the mordenite powder. Then, a honeycomb catalyst 21 was prepared by the method similar to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 22:

A powdery catalyst was prepared by impregnating an Ca-type A-zeolite powder with an aqueous solution of chloroplatinic acid to permit 0.6 part by weight of Pt to be supported by the zeolite powder. Then, a honeycomb catalyst 22 was prepared by the method similar to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 23:

A powdery catalyst was prepared by impregnating a γ-Al₂O₃ powder with an aqueous solution of chloroplatinic acid to permit 0.6 part by weight of Pt to be supported by the alumina powder. Then, a honeycomb catalyst 23 was prepared by the method similar to that described previously in conjunction with preparation of honeycomb catalyst 1.

Honeycomb Catalyst 24:

A powdery catalyst was prepared by impregnating an anatase-type TiO₂ powder with an aqueous solution of chloroplatinic acid to permit 0.6 part by weight of Pt to be supported by the TiO₂ powder. Then, a honeycomb catalyst 24 was prepared by the method similar to that described previously in conjunction with preparation of honeycomb catalyst 1.

Table 1 shows compositions of the crystalline silicate or carriers and the metals supported on the carriers in respect of the honeycomb catalysts 1 to 24 thus prepared:

Honeycomb Active Carrier catalyst No. metal No. Composition of crystalline silicate or carrier 1 Pt 1 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 2 Pt 2 0.5Na₂O.0.5H₂O[0.2Co₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 3 Pt 3 0.5Na₂O.0.5H₂O[0.2Ru₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 4 Pt 4 0.5Na₂O.0.5H₂O[0.2Rh₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 5 Pt 5 0.5Na₂O.0.5H₂O[0.2La₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 6 Pt 6 0.5Na₂O.0.5H₂O[0.2Ce₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 7 Pt 7 0.5Na₂O.0.5H₂O[0.2Ti₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 8 Pt 8 0.5Na₂O.0.5H₂O[0.2V₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 9 Pt 9 0.5Na₂O.0.5H₂O[0.2Cr₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 10 Pt 10 0.5Na₂O.0.5H₂O[0.2Sb₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 11 Pt 11 0.5Na₂O.0.5H₂O[0.2Ga₂O₃.0.8Al₂O₃.0.2CaO]25SiO9 12 Pt 12 0.5Na₂O.0.5H₂O[0.2Nb₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 13 Pt 13 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2MgO]25SiO₂ 14 Pt 14 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2SrO]25SiO₂ 15 Pt 15 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2BaO]25SiO₂ 16 Pd 1 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 17 Rh 1 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 18 Ru 1 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 19 Ir 1 0.5Na₂O.0.5H₂O[0.2Fe₂O₃.0.8Al₂O₃.0.2CaO]25SiO₂ 20 Pt 16 Y-type zeolite (molar ratio of SiO₂ to Al₂O₃ being 5.2) 21 Pt 17 Mordenite (molar ratio of SiO₂ to Al₂O₃ being 10) 22 Pt 18 A-type zeolite (molar ratio of SiO₂ to Al₂O₃ being 0.5) 23 Pt 19 γ-Al₂O₃ 24 Pt 20 Anatase type TiO₂

TABLE 2 Lattice spacing (d value) Relative intensity 11.2 ± 10.3 VS 10.0 ± 0.3  VS 6.7 ± 0.2 W 6.4 ± 0.2 M 6.0 ± 0.2 M 5.7 ± 0.2 W 5.6 ± 0.2 M 4.6 ± 0.1 W 4.25 ± 0.1  M 3.85 ± 0.1  VS 3.75 ± 0.1  S 3.65 ± 0.1  S 3.3 ± 0.1 M 3.05 ± 0.1  W 3.0 ± 0.1 M VS: very strong S: strong M: medium W: weak X-ray source: CuKα

Examples 1 to 25:

A first catalyst having an application temperature falling within a range of between 50° C. and 150° C. and a second catalyst having an application temperature higher than that of the first catalyst and falling within a range of between 150° C. and 270° C. were selected from among the honeycomb catalysts 1 to 24. Each of these CO selective oxidation catalysts 1 and 2 for low and high temperatures, respectively, was loaded in the catalyst bed in an amount of 15 cc, totaling 30 cc of the catalysts 1 and 2, to form a catalyst bed 3 in which these first catalyst layer 1 and second catalyst layer 2 were connected in series, as shown in the FIGURE appended hereto.

A sample gas containing 1.0% of CO, 24% of CO₂, 20% of H₂O, 0.7% of O₂ and 54.3% of H₂ was introduced into the catalyst bed 3 through the catalyst layer 1 of a low application temperature with GHSV (gas hourly space velocity) set at 20,000 h⁻¹ (gas amount of 600 NL/h) so as to perform a first carbon monoxide removal from the sample gas. During the test, the CO concentration at the outlet port of the catalyst bed 3 was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Tables 3 and 4 also show the results together with the temperature of the sample gas at the inlet of the catalyst bed and the temperature of the sample gas at the outlet of the first selective CO oxidizing catalyst layer 1 on the upstream side.

Then, 0.3% of an additional O₂ was added to the sample gas, followed by introducing the sample gas into the selective CO oxidizing catalyst layer 2 for a high application temperature at GHSV (gas hourly space velocity) of 20,000 h⁻¹ (gas amount of 600 NL/h) so as to carry out a second carbon monoxide removal. During the test, the CO concentration at the outlet port of the catalyst bed 3 was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Tables 3 and 4 also show the results together with the temperature of the sample gas at the outlet port of the second CO selective oxidizing catalyst layer 2 for a high application temperature (the temperature of the sample gas at the outlet of the catalyst bed).

COMPARATIVE EXAMPLES 1 TO 3

One kind of a catalyst was selected from among the honeycomb catalysts 1 to 24 and the catalyst thus selected was used both as catalysts 1 and 2. The amount of each of these catalysts 1 and 2 was 15 cc, totaling 30 cc of catalysts 1 and 2. These catalysts 1 and 2 were arranged as shown in the FIGURE to form the catalyst bed 3. A sample gas of the composition equal to that of the sample gas used in Examples 1-25 was introduced into the catalyst bed 3 through the catalyst layer 1 with GHSV (gas hourly space velocity) set at 20,000 h⁻¹ (gas amount of 600 NL/h) so as to a first carbon monoxide removal from the sample gas. During the test, the CO concentration at the outlet port of the catalyst bed 3 was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Table 4 shows the results together with the temperature of the sample gas at the inlet of the catalyst bed and the temperature of the sample gas at the outlet of the first selective CO oxidizing catalyst layer 1 on the upstream side.

Then, 0.3% of an additional O₂ was added to the sample gas, followed by introducing the sample gas into the second selective CO oxidizing catalyst layer at GHSV (gas hourly space velocity) of 20,000 h⁻¹ (gas amount of 600 NL/h) so as to carry out a second carbon monoxide removal. During the test, the CO concentration at the outlet port of the second catalyst layer was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Table 4 also shows the results together with the temperature of the sample gas at the outlet port of the second CO selective oxidizing catalyst layer 2 (the temperature of the sample gas at the outlet of the catalyst bed).

TABLE 3 Low temperature side High temperature side Inlet Outlet Outlet tempera- tempera- CO concentra- tempera- CO concentra- Honeycomb ture of ture of tion at Honeycomb ture cf tion at catalyst catalyst catalyst outlet of catalyst catalyst outlet of (active layer layer catalyst (active layer catalyst metal) (° C.) (° C.) layer (ppm) metal) (° C.) layer (ppm) Example 1 1 (Pt) 100 160 1200 18 (Ru) 190 13 Example 2 2 (Pt) 97 164 1300 18 (Ru) 192 13 Example 3 3 (Pt) 98 164 1400 18 (Ru) 193 11 Example 4 4 (Pt) 95 160 1340 18 (RU) 195 10 Example 5 5 (Pt) 93 156 1500 18 (Ru) 196 9 Example 6 6 (Pt) 92 155 1800 18 (Ru) 195 10 Example 7 7 (Pt) 95 156 1600 18 (Ru) 189 11 Example 8 8 (Pt) 101 159 1560 18 (Ru) 192 10 Example 9 9 (Pt) 103 162 1450 18 (Ru) 193 10 Example 10 10 (Pt) 101 164 1540 18 (Ru) 195 9 Example 11 11 (Pt) 100 164 1500 18 (Ru) 196 11 Example 12 12 (Pt) 97 165 1490 18 (Ru) 198 10 Example 13 13 (Pt) 93 160 1500 18 (Ru) 198 9 Example 14 14 (Pt) 94 160 1450 18 (Ru) 187 11

TABLE 4 Low temperature side High temperature side Inlet Outlet CO Outlet tempera- tempera- concentra- tempera- CO concentra- Honeycomb ture of ture of tion at Honeycomb ture of tion at catalyst catalyst catalyst outlet of catalyst catalyst outlet of (active layer layer catalyst (active layer catalyst metal) (° C.) (° C.) layer (ppm) metal) (° C.) layer (ppm) Example 15 15 (Pt) 96 159 1500 18 (Ru) 196 10 Example 16 16 (Pd) 140 185 4700 18 (Ru) 208 32 Example 17 17 (Rh) 135 175 3900 18 (Ru) 205 23 Example 18 19 (Ir) 135 165 1850 18 (Ru) 204 17 Example 19 20 (Pt) 100 165 2600 18 (Ru) 193 22 Example 20 21 (Pt) 105 168 2500 18 (Ru) 194 27 Example 21 22 (Pt) 99 160 2700 18 (RU) 196 31 Example 22 23 (Pt) 102 158 2900 18 (Ru) 193 29 Example 23 24 (Pt) 99 161 2700 18 (Ru) 198 30 Example 24 1 (Pt) 96 154 1500 19 (Ir) 193 34 Example 25 20 (Pt) 99 158 2500 19 (Ir) 193 45 Comparative 1 (Pt) 96 160 1550 1 (Pt) 199 80 example 1 Comparative example 2 18 (Ru) 105 155 5500 18 (Ru) 199 103 Comparative 19 (Ir) 125 155 1950 19 (Ir) 196 105 example 3

As apparent from Tables 3 and 4, in Examples 1 to 25, in which two kinds of catalysts 1 and 2 differing from each other in the application temperature were arranged such that the catalyst layer 1 having a low application temperature was arranged on the upstream side and a sample gas containing H₂, O₂ and CO was passed through the catalyst bed 3 from the catalyst layer 1 having a low application temperature, followed by introducing the sample gas into the second catalyst layer 2 having a high application temperature after supply of an additional O₂ into the sample gas, it was possible to lower markedly the high CO concentration of 1.0% in the sample gas to 50 ppm or lower. However, in Comparative Examples 1 to 3, in which the catalyst layers 1 and 2 of the catalyst bed 3 were formed of the same catalyst having Pt, Ir or Ru supported as an active metal on the carrier, the CO concentration at the outlet of the catalyst bed 3 was found to be higher than that in Examples 1 to 25.

EXAMPLES 26 TO 28

Three kinds of catalysts differing from each other in the application temperature were selected from among the honeycomb catalysts 1 to 24 and arranged in series in the order of the application temperature such that the honeycomb catalyst having a low application temperature was arranged on the upstream side so as to form the catalyst bed. Table 5 shows the kinds of the honeycomb catalysts constituting the three catalyst layers of the catalyst bed. The amount of each of these three catalysts was 15 cc, totaling 45 cc of the catalysts.

A sample gas containing 1.0% of CO, 24% of CO₂, 20% of H₂O, 0.5% of O₂ and 54.5% of H₂ was introduced into the catalyst bed 3 through the first catalyst layer of a low application temperature with GHSV (gas hourly space velocity) set at 15,000 h⁻¹ (gas amount of 450 NL/h) so as to perform a first carbon monoxide removal from the sample gas. During the test, the CO concentration at the outlet port of the first catalyst layer was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Table 5 show the results together with the temperature of the sample gas at the inlet of the catalyst bed and the temperature of the sample gas at the outlet of the first CO selective oxidizing catalyst layer for a low application temperature.

Then, 0.3% of an additional O₂ was added to the sample gas, followed by introducing the sample gas into the second selective CO oxidizing catalyst layer for an intermediate application temperature at GHSV (gas hourly space velocity) of 15,000 h⁻¹ (gas amount of 450 NL/h) so as to carry out a second carbon monoxide removal. During the test, the CO concentration at the outlet port of the second catalyst layer was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Table 5 also shows the results together with the temperature of the sample gas at the outlet port of the second CO selective oxidizing catalyst layer for an intermediate application temperature.

Further, 0.1% of an additional O₂ was added to the sample gas, followed by introducing the sample gas into the third selective CO oxidizing catalyst layer for a high application temperature at GHSV (gas hourly space velocity) of 15,000 h⁻¹ (gas amount of 450 NL/h) so as to carry out a third carbon monoxide removal. During the test, the CO concentration at the outlet port of the third catalyst layer was continuously monitored by a ND-IR type CO meter and the CO concentration was measured when the CO concentration was stabilized. Table 5 also shows the results together with the temperature of the sample gas at the outlet port of the third CO selective oxidizing catalyst layer for a high application temperature (the temperature of the sample gas at the outlet of the catalyst bed).

TABLE 5 Low temperature side Intermediate temperature side Inlet Outlet CO Outlet tempera- tempera- concentra- tempera- CO concentra- Honeycomb ture of ture of tion at Honeycomb ture of tion at catalyst catalyst catalyst outlet of catalyst catalyst outlet of (active layer layer catalyst (active layer catalyst metal) (° C.) (° C.) layer (ppm) metal) (° C.) layer (ppm) Example 26 1 (Pt) 95 145 2200 19 (Ir) 180 45 Example 27 20 (Pt) 97 152 3500 19 (Ir) 175 65 Example 28 1 (Pt) 98 155 2400 17 (Rh) 179 67 High temperature side Honeycomb Outlet CO concentration catalyst temperature at outlet of (active of catalyst catalyst layer metal) layer (° C.) (ppm) Example 26 18 (Ru) 195  7 Example 27 18 (Ru) 198 11 Example 28 18 (Ru) 196 10

As apparent from Table 5, the high CO concentration of the sample gas, which was 1.0%, was lowered to 11 ppm or less in Examples 26 to 28, in which three kinds of catalysts differing from each other in the application temperature were arranged in series in the order of the application temperature such that the catalyst having a low application temperature was arranged on the upstream side so as to form the catalyst bed and a sample gas containing H₂, CO and an oxidizing gas of O₂ was passed through the catalyst bed from the catalyst layer having a low application temperature, and an additional O₂ was supplied to the sample gas every time the sample gas coming from the first catalyst layer was introduced into the second catalyst layer having an intermediate application temperature and, then, into the third catalyst layer having a high application temperature.

In the Examples described above, the crystalline silicate carrier of the catalyst capable of selectively oxidizing carbon monoxide was of H-type. However, it has also been confirmed that it is possible to obtain the similar effects in the case of using a catalyst capable of selectively oxidizing carbon monoxide, said catalyst having a crystalline silicate carrier represented by aforementioned formula (1) in a dehydrated state in which R represents an alkali metal or a composition of an alkali metal and proton.

Also, in the Examples described above, the catalyst bed was prepared by arranging in series two or three kinds of catalysts capable of selectively oxidizing carbon monoxide. If four or more kinds catalysts are arranged in series to form a catalyst bed, the carbon monoxide removal rate can be further increased.

As described above in detail, the present invention provides a method of selectively removing carbon monoxide from a gaseous mixture containing H₂ and CO, which permits a high carbon monoxide removal rate.

Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents. 

What is claimed is:
 1. A method of selectively removing carbon monoxide, comprising: preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and said plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and introducing a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ into said catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a higher application temperature so as to selectively oxidize and remove CO from the gaseous mixture; wherein said plurality of catalyst layers comprises: a first catalyst layer comprising a carrier and Pt as an active metal and supported on said carrier; and a second catalyst layer comprising a carrier and Ir supported on said carrier.
 2. The method of selectively removing carbon monoxide according to claim 1, wherein said carrier of said first and second catalyst layers is selected from the group consisting of Y-zeolite, mordenite, A-zeolite, γ-Al₂O₃, anatase and a crystalline silicate having the highest to the fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, said crystalline silicate having the composition represented by formula (1) under a dehydrated state: (1±0.8)R₂O.(aM₂O₃.bNO.cAl₂O₃).ySiO₂  (1) where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000.
 3. The method of selectively removing carbon monoxide according to claim 1, wherein the temperature of said gaseous mixture falls within a range of between 50° C. and 280° C. when the gaseous mixture is introduced into the catalyst bed.
 4. The method of selectively removing carbon monoxide according to claim 1, wherein the CO concentration of said gaseous mixture is not higher than 4%.
 5. The method of selectively removing carbon monoxide according to claim 1, wherein said first catalyst layer is provided on a most upstream side of said catalyst bed.
 6. The method of selectively removing carbon monoxide according to claim 1, wherein said first catalyst layer and said second catalyst layer are arranged in the order of said first catalyst layer and said second catalyst layer from an upstream side of said catalyst bed.
 7. The method of selectively removing carbon monoxide according to claim 1, wherein said catalyst bed further comprises a third second catalyst layer comprising a carrier and Ir supported on said carrier; wherein said first catalyst layer is upstream of said second catalyst layer; and wherein said second catalyst layer is upstream of said third catalyst layer.
 8. A method of selectively removing carbon monoxide, comprising: preparing a catalyst bed capable of selectively oxidizing carbon monoxide and including a plurality of catalyst layers arranged in series and said plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and introducing a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ into said catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a higher application temperature so as to selectively oxidize and remove CO from the gaseous mixture; wherein at least one of the catalyst layers comprise a carrier and an active metal supported on said carrier, said carrier comprising a crystalline silicate having the highest to fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, said crystalline silicate having the composition represented by formula (1) under a dehydrated state: (1±0.8)R₂O·(aM₂O₃·bNO·cAl₂O₃)·ySiO₂  (1) where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000.
 9. The method of selectively removing carbon monoxide according to claim 8, wherein said crystalline silicate exhibits the highest to the eleventh highest peaks in a powder X-ray diffraction using a CuKα ray in the lattice spacing of 3.0±0.1 Å, 3.3±0.1 Å, 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 4.25±0.1 Å, 5.6±0.2 Å, 6.0±0.2 Å, 6.4±0.2 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively.
 10. The method of selectively removing carbon monoxide according to claim 8, wherein said crystalline silicate exhibits the highest to the fifteenth highest peaks in a powder X-ray diffraction using a CuKα ray in the lattice spacing of 3.0±0.1 Å, 3.05±0.1 Å, 3.3±0.1 Å, 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 4.25±0.1 Å, 4.6±0.1 Å, 5.6±0.2 Å, 5.7±0.2 Å, 6.0±0.2 Å, 6.4±0.2 Å, 6.7±0.2 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively.
 11. The method of selectively removing carbon monoxide according to claim 8, wherein said active metal comprises at least one metal selected from the group consisting of Pt, Pd, Ru, Rh and Ir.
 12. The method of selectively removing carbon monoxide according to claim 8, wherein the temperature of said gaseous mixture falls within a range of between 50° C. and 280° C. when the gaseous mixture is introduced into the catalyst bed.
 13. The method of selectively removing carbon monoxide according to claim 8, wherein the CO concentration of said gaseous mixture is not higher than 4%.
 14. A method of selectively removing carbon monoxide comprising: preparing a catalyst bed capable of selectively removing carbon monoxide and including a plurality of catalyst layers arranged in series and said plurality of catalyst layers differing from each other in the temperature of application and arranged in the order of the application temperature such that the catalyst layer having the lowest application temperature constitutes the upstream side of the catalyst bed; and introducing a gaseous mixture containing H₂, CO and an oxidizing agent of O₂ into said catalyst bed through the upstream side of the catalyst bed and supplying an additional oxidizing agent to the gaseous mixture when the gaseous mixture is introduced into the catalyst layer having a higher application temperature so as to selectively oxidize and remove CO from the gaseous mixture, said plurality of catalyst layers comprising: a first catalyst layer having a high application temperature comprising a carrier and at least one active metal selected from the group consisting of Pd, Ru, Rh and Ir supported by said carrier; a second catalyst layer having a low application temperature comprising a carrier and Pt supported by said carrier; and a third catalyst layer having an intermediate application temperature, arranged between said first and second catalyst layers, said third catalyst layer comprising a carrier and at least one active metal selected from the group consisting of Pd, Ru, Rh and Ir supported by said carrier.
 15. The method of selectively removing carbon monoxide according to claim 14, wherein said carrier in each of said first, second and third catalyst layers is independently selected from the group consisting of Y-zeolite, mordenite, A-zeolite, γ-Al₂O₃, anatase and a crystalline silicate having the highest to fifth highest peaks in the powder X-ray diffraction using CuKα ray in the lattice spacing of 3.65±0.1 Å, 3.75±0.1 Å, 3.85±0.1 Å, 10.0±0.3 Å, and 11.2±0.3 Å, respectively, said crystalline silicate having the composition represented by formula (1) under a dehydrated state: (1±0.8)R₂O·(aM₂O₃·bNO·cAl₂O₃)·ySiO₂  (1) where R denotes at least one element selected from the group consisting of an alkali metal and H, M denotes at least one element selected from the group consisting of VIII group elements, rare earth elements, Ti, V, Cr, Nb, Sb and Ga, N denotes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and the molar ratios a, b, c and y are: 0≦a, 0≦b≦20, a+c=1, and 11≦y≦3000. 